Non-fluoro hydrophobic aqueous-based polyurethane resin dispersion

ABSTRACT

The present invention provides a cross-linking non-fluoro hydrophobic aqueous polyurethane dispersion, which is produced by selecting a compound comprising alcohols, amines, acids, saturated or unsaturated (double-bonded or epoxidized) aliphatic long chain carbon-carbon groups or polydimethylsiloxane comprising alcohol groups, amines, oxosilane to be reacted with IPDI to obtain a PU prepolymer; adding a compound having tertiary amines to neutralize the carboxylic acid of PU prepolymer and adding water to disperse the PU prepolymer; and adding a ambient temperature cross-linking agent to obtain a cross-linking hydrophobic aqueous PU dispersion of the present invention. The hydrophobic aqueous-based PU resin has no fluorine which is friendly to the environment, and may further self cross-links on its applications on fabric, paper, wood, glass and metal surfaces, respectively on drying at ambient temperature which is energy saving process. Its cross-linking reaction of this hydrophobic PU system that will achieve a long-lasting water repellent surface treatment.

BACKGROUND

The present invention relates to aqueous polyurethane (PU) dispersion,and its production method and use, especially a non-fluoro, hydrophobicaqueous PU dispersion, and its production method and use.

Nowadays, the public places importance on outdoor activities, sports andwork out. Regarding the dressing while doing exercise, the requirementsfor a functional dress are light, convenient and comfortable. Hence,this kind of functional dressing becomes the main business of thedevelopment. Generally, an outdoor dressing for user to feel comfortableusually requires a water-repellent surface, i.e. its materials havehydrophobic properties, and a property for releasing the moisture fromhuman body at the same time, i.e. the fabric having a breathablefunction (moisture permeation and sweat release). This kind of productis needed in the current market.

The fabric having a function of moisture permeation and sweat release,which has been sold in market, uses the fabric which isfluoro-containing resin processed, i.e. fluoro-containing acrylic resinor PTFE (polytetrafluoroethylene) attached film. However, thesematerials already reach its limitation of water-repellent fabric in theaspect of resistance. In addition, no matter using fluoro containingresin or PTFE attached film as material for water-repellent treatment,these materials all have C8-fluoro compounds, PFOA (perfluoro-octanoicacid) or PFOS (perfluoro-octanesulfonic acid) salt and the like. Thesecompounds are certified causing carcinogenesis. Hence, the waterrepellent having C8-fluoro compounds is eliminated gradually, and willbe prohibited from 2015. Although there are low carbon (such as C6 orC4) flour-compounds used in market as flour-containing water repellent,in order to achieve to an expected water-repellent efficacy, the usageof low carbon flour-containing compounds require a higher amount thanC8-flour-compounds do. This situation is expected to cause an impact toenvironment, especially the accumulation in alive organism, and furthermay cause the defects for considering the damage of ecologicalenvironment of earth.

In addition, the resin used in resin having flour-containing nowadays isacrylic-based resin mainly. When applying it to the coating process,this kind of resin cannot process the following cross-linking reaction.Hence, the processed products of resin having flour-content cannotmaintain long-term efficacy of water repellent, and this is a problemwhich the fabric for treating water repellent needs to be dealt with.However, if the method of attached film is carried out, it is necessaryfor using specific extended PTFE film materials, specific dispensingglue and the facility for attaching film to carry out the process ofattaching film for water-repellent fiber. Regarding the cleaning inaspect of customers, it requires specific professional method to cleanit and that would be another inconvenience.

Generally, the water-repellent fabric in the market would have thefollowing defects:

1. The bad hand-feel: Using the coating of water repellent havingacrylic resin fluoro or PTFE attached film on the surface of fibercauses the stiff feeling when touching the fabric.

2. The poor washing durability: After the process of water-repellentcoating, the known water-repellent fabric is only covered by the waterrepellent on its surface, instead of polymeric inter-penetratingnetworks (IPN) anchoring in fabric and forming between fabric yarns.Hence, after multiple times of use, it is easy to damage the fabric dueto rubbing and washing, further to decrease the water-repellentfunction. The fabric has the durability decrease.

3. Poor Breathability: The processes material, such as water repellent,is covered on the surface of fabric by the coverage method. Due tooverdose of resin coating on, the excess amount of resin plugs thefabric and decreases the original air permeability of fabric. The fabrichas the defect on breathability.

4. The cost of protecting environment is too high: In the knownknowledge, no matter using the method of coating or attached film, itrequires a fluoro-containing polymer that can cause pollution loading,bio-toxicity and the accumulation in alive organism to environment. Thefabric has the defect that cause damage to ecology of earth.

To sum up, it is necessary to develop a water repellent havingnon-fluoro compounds which is valuable and the water repellent needs tobe improved urgently.

SUMMARY OF THE INVENTION

The present invention selects non-fluoro compounds and non-toxiccompounds having reactive functional groups individually, such as thecompounds having hydrophobic property, like aliphatic compounds, i.e.aliphaltic long chain carbon-carbon bonding compounds, or PDMS(polydimethylsiloxane) and the like. As the reactive materials ofaqueous polyurethane (PU) resin, a “latent cross-linking (curing) agent”is added, and successfully develops “single-component cross-linkingnon-fluoro hydrophobic aqueous polyurethane (PU) dispersion”. Whencarrying out applying, i.e. while drying or the pH value of dispersiondrops less than 7.0, PU resin would generate a cross-linking reactionwith the latent cross-linking agent to increase the cross-linkingdensity of this hydrophobic PU resin, and further to improve washingresistance and solvent resistance of hydrophobic polyurethane resin toreach a long-term hydrophobic (water-repellent) function.

The non-fluoro hydrophobic aqueous polyurethane dispersion havinglong-term water-repellent function of the present invention comply therequirements of energy saving and carbon dioxide reduction and isexpected to replace the fluoro-containing water repellent which is goingto be eliminated.

The technical characteristics of the present invention mainly areselecting separately or mix-using a compound comprising alcohols,amines, acids, saturated or unsaturated (double-bonded or epoxidized)aliphatic acids which have reactive aliphatic long chain carbon-carbonbond, for instance, ricinoleic acid, fatty acid ester or oleic acid, ora hydrophobic compound, for instance, polydimethylsiloxane containingalcohol groups, amino groups or oxosilane groups, to react withployiscyanate as reactive material of hydrophobic polyurethane (PU)resin. In addition, in the material of PU resin, adding compoundscontaining hydrophilic group (such as COOH) to PU resin. Afterneutralizing, it would provide a self-emulsified hydrophilic ioniccenter for PU resin. While adding water to disperse the PU prepolymer,it would form “Self-emulsified Non-fluoro Hydrophobic Aqueous PUdispersion”. Further adding a suitable amount of cross-linking agent(such as TMPTA-AZ or CX-100) to form a stable “single-componentcross-linking form” aqueous PU dispersion (its pH value maintaining 8.0or higher belongs stable emulsion). While drying on application (orwhile the pH value is less than 7.0), i.e. when the ionic groups (COOH)in PU resin and the reactive functional groups (such as aziridine) ofcross-linking (curing) agent under room-temperature and dry condition,it would generate a ring-opening cross-linking reaction to increase thecross-linking density in order to improve washing resistance and solventresistance. The hydrophobic polyurethane resin has a long lastinghydrophobic (water-repellent) function. In the present specification, itwould refer this kind of hydrophobic PU as “single-componentcross-linking non-fluoro hydrophobic aqueous PU dispersion”.

The “single-component cross-linking non-fluoro hydrophobic aqueous PUdispersion” of the present invention has reactive hydrophobic aqueous PUresin, which it can generate interpenetrating polymeric networks (IPN)by self-crosslink reaction to insert between fabric (such aslongitudinal yarn and latitudinal yarn), wood, or the fiber of paper andform physical insertion or even chemical bonding under room temperature.The cross-linking reaction of the components of this new invention cancarry out under room temperature, and can use a single component or anymixing ratio of aliphatic long chain carbon-carbon bond or PDMS as ahydrophobic PU modified components, especially that the amount ofhydrophobic groups requires less amount (5-10%) to reach thewater-repellent efficacy.

The non-fluoro hydrophobic PU dispersion of the present invention iscoated on the surface of the fabrics by simple coating method (by amethod of scraper, roller, impregnation, spray or screen printing andthe like), and dried under room temperature to achieve the cross-linkinglong-term hydrophobic PU resin coating. The processed fabric maintains85% of the original water-repellent efficacy after washed (after 50washing cycles) in the test of static contact angle and dynamic slidingangle of water drops.

The present invention provides a production method of non-fluorohydrophobic aqueous dispersion comprising the following steps: selectinga compound comprising alcohols, amines, acids, saturated or unsaturated(double-bonded or epoxidized) aliphatic groups or polydimethylsiloxane(PDMS) comprising alcohol groups, amino groups, oxosilane groups to bereacted with 3-Isocyanato-methyl-3,5,5-trimethylcyclohexyl isocyanate toobtain a PU prepolymer having NCO terminal group; after neutralizing,adding water to disperse the PU prepolymer to obtain an aqueous PUdispersion; and adding a cross-linking (curing) agent into the aqueousPU dispersion to obtain an ambient temperature self linking aqueous PUdispersion.

Preferably, the unsaturated aliphatic groups have functional groups ofalcohol groups, amino groups, carboxyl groups or double bond.

Preferably, the average molecular weight of polydimethylsiloxane is500-3000, and polydimethylsiloxane has reactive functional groups ofalcohol groups, amino groups, carboxyl groups, epoxy groups, oxosilanegroups or double bond.

Preferably, the aliphatic containing alcohol group is higher alcohols ordiols having carbon numbers from 10 to 30.

Preferably, the aliphatic containing amino group is the compound havingcarbon number from 10 to 30.

Preferably, the aliphatic containing double bond is castor oil, palmoil, soybean oil or epoxidized soybean oil.

Preferably, the cross-linking agent is poly-aziridine cross-linkingagent.

Preferably, the aqueous polyurethane dispersion which reacts thecross-linking agent comprises aliphatic of aliphatic acids having carbonnumber from 10 to 30.

Preferably, the polydimethylsiloxane group of the cross-linked aqueouspolyurethane-dispersion is on the main chain or side chain ofpolyurethane resin.

The present invention also provides a non-fluoro hydrophobic aqueouspolyurethane dispersion, wherein the polyurethane dispersion obtained bythe aforementioned production method.

Preferably, the polyurethane dispersion can be made into single-liquidform.

The present invention further provides an use of water repellent applieda polyurethane dispersion, wherein the polyurethane dispersion obtainedby the aforementioned production method or is the aforementionedpolyurethane dispersion.

Preferably, the polyurethane dispersion is applied on an object which isgoing to be coated under pH value less than 7 to make the carboxylatereactive functional groups comprised react with a cross-linking agent togenerate a ring-opening cross-linking reaction.

Preferably, the object which is going to be coated has hydroxyl groups,carboxylic acids, epoxy groups or amino groups.

Preferably, the silane groups comprised in the polyurethane dispersionreacts with hydroxyl groups or amino groups of the object which is goingto be coated to form chemical bonding.

Preferably, the polyurethane dispersion can be coated on a surface ofthe object which is going to be coated by a method of scraper, roller,impregnation, spray or screen printing and the like.

By using the non-fluoro hydrophobic aqueous PU resin of the presentinvention, it can reach the following advantages and efficacy:

1. A self-emulsified (having internal ionic groups) aqueous PUdispersion.

2. Being non-fluoro (non-toxic aliphatic long chain carbon-carbon bondcompounds or polydimethylsiloxane) and hydrophobic.

3. The self-linking procedure for energy saving and carbon dioxidereduction which may be self cross-linked (under room-temperature driedor pH value being less than 7.0) provides the functions of washingresistance, solvent resistance and long lasting hydrophobic efficacy.

4. PU resin may flexibly adjust the softness and density to provide longlasting hydrophobic (water-repellent) properties.

5. Both of hydrophobic molecular chain domain (groups) aliphatic longchain carbon-carbon bond aliphatics (or fatty acids) andpolydimethylsiloxane (PDMS) can be used alone and also can be usedtogether (in different ratios) to achieve complementary hydrophobicproperties.

DESCRIPTION OF FIGURES

FIG. 1 displays a SEM micrograph of the fiber treated by aqueous PUdispersion containing aliphatic acids and PDMS which are mixed andreacted (unwashed);

FIG. 2 displays a EDS of the fiber treated by aqueous PU dispersioncontaining aliphatic acids and PDMS which are mixed and reacted(unwashed);

FIG. 3 displays a SEM micrograph of the fiber treated by aqueous PUdispersion containing aliphatic acids and PDMS which are mixed andreacted (after 40 washing cycles); and

FIG. 4 displays an EDS of the fiber treated by aqueous PU dispersioncontaining aliphatic acids and PDMS which are mixed and reacted (after40 washing cycles) (still have silicon on the surface of fiber).

DETAILS OF THE INVENTION

The present invention is described in details by the followingembodiments and figures to clarify the production method for non-fluorohydrophobic aqueous PU dispersion and the application of water-repellenttreatment thereof.

(1) The Preparation of Isocyanate Terminated Polyurethane (PU)Prepolymer

Taking 13.4 g of 2,2′-bis(hydroxymethyl) propionic acid (DMPA) and 200 gof polytetramethylene ether glycol (PTMEG-2000) separately and placingthem into four-necked reaction tank, and heating to 140° C. to melt DMPAand stirring it with mechanical agitation evenly. Wait for thetemperature drop to 50° C., adding 0.1%(w/w) reactive catalyst T-12 and66.6 g of isophorone diisocyanate (IPDI) and keep reaction temperaturebelow 86° C. with stirring until the reaction is completed (NCO % belowthe calculated value). After the reaction is completed, processing NCOtitration to analyze the degree of reaction, as long as it reaches NCO %is less than 3% and remains at that value for one hour. Further usingFT-IR to determine the presence of the NCO peak (near 2267 cm⁻¹) inorder to make sure that if the reaction is completed or not. Thereaction scheme is as the aforementioned scheme 1.

(2) The Preparation of “Self-Emulsified Aliphatic Long ChainCarbon-Carbon Bond Containing Aqueous PU Dispersion”

Selecting polyether polyol (for instance, PPG or PTMEG), polyisocyanate(IPDI) materials, or diol compounds containing hydrophilic functionalgroups as internal emulsifier (for instance, dimethylol propanic acid,DMPA) and fatty alcohols (aliphatic long chain carbon-carbon bondalcohol compounds). A long chain carbon-carbon bond containing PUprepolymer having isocyanate as terminal groups (with fatty alcoholsinvolved in the reaction). Determine the amount of NCO to confirm thatthe reaction is completed, and adding triethylamine to neutralize andadding deionized water and chain extender (such as ethylenediamine) toprocess the steps of chain extension and dispersion, and theself-emulsified aliphatic long chain carbon-carbon bond containingaqueous PU dispersion is obtained. In this aqueous PU dispersion, addingproper quantity cross-linking agent (TMPTA-AZ or CX100) and maintain thepH value of aqueous PU dispersion system greater than 8.0. The stable“self-emulsified aliphatic long chain carbon-carbon bond containingaqueous PU dispersion” is formed. The details of the preparation schemeplease refer to the following scheme 2.

(3) The Preparation of Room-Temperature Cross-Linked “Single-LiquidNon-Fluoro Hydrophobic Aliphatic Acid (Ester)-Contained Aqueous PUDispersion”

Selecting polyether polyol (PPG or PTMEG), polyisocyante (IPDI)materials, or diol compounds containing hydrophilic functional groups asinternal emulsifier (DMPA) and high carbon-carbon aliphatic acidcompounds to process PU resin. A long chain fatty acid containing PUprepolymer having isocyanate as terminal-ended group (with hydroxyl orepoxidized fatty acid involved in the reaction). This aliphatic PUprepolymer having isocyanate (NCO) as terminal-ended group, and addingaliphatic acids (as stearic acid, oleic acid, epoxidized oleic acid orricinoleic acid) alone or proper ratio separately in PU prepolymer. Thenadding triethylamine to neutralize and adding deionized water and chainextender (such as diethylamine) to process the steps of chain extensionand dispersion (aliphatic fatty acid becomes soap after neutralizationwhich have emulsified efficacy), and the self-emulsified aliphaticsoap-containing aqueous-based PU dispersions is obtained. In thisaqueous PU dispersion, adding proper quantity latent cross-linking agent(TMPTA-AZ or CX100) and maintain the pH value of aqueous PU dispersionmore than 8.0. The stable “self-emulsified fatty acid-containing aqueousPU dispersion” is formed.

(4) The Preparation of Room-Temperature Cross-Linked “Single-LiquidNon-Fluoro Hydrophobic Polydimethylsiloxane-Contained Aqueous PUDispersion”

Selecting polyether polyol (PPG or PTMEG), polyisocyante (IPDI)materials, or diol compounds containing hydrophilic functional groups asinternal emulsifier (DMPA) and polydimethylsiloxane(PDMS)-containingdiol are added to process PU resin. The PDMS-containing PU prepolymerhaving isocyanate as terminal-ended group, and then adding triethylamineto neutralize and adding deionized water and chain extender (such asdiethylamine) to process the steps of chain extension and dispersion,and “self-emulsified polydimethylsiloxane-containing aqueous PUdispersion” is obtained. The details of the preparation scheme pleaserefer to the following scheme 3.

(5) The Room-Temperature Bridge Reaction of “Single-Liquid Non-FluoroHydrophobic Aqueous PU Dispersion”

Regarding the “single-component hydrophobic aqueous PU dispersion” ofthe present invention, the fatty (alcohol or acid) orpolydimethylsiloxane (PDMS)-containing aqueous PU dispersion isintroduced carboxylic acid group (COOH) separately. After neutralizationand dispersion by adding water under a high speed mechanical mixing, theionic group (carboxyl groups, COO—) induced is used as internalemulsifier to provide the stability of aqueous PU dispersion. The latentcross-linking agent containing aziridine functional groups (as TMPTA-AZor CX-100) added into “single-liquid non-fluoro hydrophobic aqueous PUdispersion” would react with carboxyl groups in PU resin to processopen-ring cross-linking reaction under room temperature being dried atambient temperature. It would react with hydrophilic carboxyl groups andform hydrophobic amino ester bonding, and improve the cross-linkingdensity of aqueous PU resin on drying. The water resistance, solventresistance, mechanical strength and heat stability would be improvedaccordingly. Due to the aziridine functional groups contained in aqueousPU as a latent cross-linking agent having high pH value, aziridine canpresent in water dispersion stably. When under low pH value (<7.0),aziridine would process open-ring reaction with carboxylic acid (COOH)in PU resin or process open-ring reaction itself under room temperaturewithout heating or other energy (the radiation of UV). The details ofthe cross-linking (curing) reaction please refer to the following scheme4.

(6) The Treatment of Water-Repellent Coating

The aqueous PU dispersion containing different amount ofpolydimethylsiloxane (PDMS) or aliphatic acid or fatty alcohol is coatedby a simple method (scraper, roller, impregnation, spray or screenprinting and the like) to process the treatment of water-repellent onthe surface of fabric. Under the condition of room temperature, theself-curing (cross-linking) reaction is carried out to form PU resinwith interpenetrating networks (IPN) structure tightly and anchoredbetween longitudinal yarn and latitudinal yarn of the fabric, so that itimprove the durability of water washing of water-repellent resin treatedfabric. After the washing test of National Standard AATCC135-2004 towash it for 40 cycles, it still remains 85% of the originalwater-repellent efficacy. This kind of water-repellent PU resin requiresonly small amount (5-15% solid contents) for coating to achievewater-repellent efficacy.

The present invention is clarified by preferable specific embodimentswhich are not used to limit the present invention.

The synthesis and preparation of self-emulsified aliphatic long chaincarbon-carbon bond containing aqueous PU dispersions

Using different polyols of polymer and polyisocyantes materials, diolcompounds containing hydrophilic functional groups as internalemulsifier (such as ionic internal emulsifier and non-ionic internalemulsifier) and fatty alcohol of long chain carbon-carbon aliphaticalcohols compounds to process addition polymerization reaction bydifferent formulating method. The aliphatic long chain carbon-carbon PUoligomer and prepolymer used isocyanate as terminal-ended groups areformed. Further neutralization by a tertiary amine deionized water andchain extender to process the steps of chain extension and waterdispersion with mechanical agitation. It results in a formation ofself-emulsified aliphatic carbon-carbon chain containing aqueous-basedPU dispersions.

The materials which are needed to synthesize self-emulsified aliphaticcarbon-carbon chain containing aqueous-based PU dispersions are listedas following:

1. Polyols

The property of polyurethane elastomers is due to the chain structurehaving flexibility and the structure of minor branching or partial netcross-linking Polyols with better flexibility are polyesters,polyethers, polyether-ester polyols or polyester-amide polyols and thelike.

(a) Polyester Polyols:

(b) Polyether Polyols (PP): The common polyether polyols are asfollowing: polyethylene glycols, polypropylene glycols,polytetramethylene glycols which have the average molecular weightranging in 400-4000.

2. Polyisocyantes

The most common diisocyante is toluene diisocyanates (TDI),hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI),4,4-methylene diphenyl diisocyanate (MDI) and the like. In aromaticdiisocyanates, the main toluene diisocyanates in the market comprise:80% of 2,4-toluene diisocyanates (TDI) and 20% of 2,6-toluenediisocyanates (TDI). In the 2,4-toluene diisocyanates molecule, theactivity of para-(4-) isocyanate functional groups is higher thanortho-(2-,6-) ones by 4 to 5 times. It benefits for producing selectiveisocyanate prepolymer.

In addition, in aliphatic diisocyanates, two isocyanate functionalgroups in isophorone diisocyanate (IPDI) show different activity.Without the influence of catalyst, secondary isocyanate functionalgroups (2°-NCO) have higher reaction rate than the one of primaryisocyanate functional groups (1°-NCO). Surprisingly, after adding minortin catalyst, secondary isocyanate functional groups (2°-NCO) havehigher reaction rate than the one of primary isocyanate functionalgroups (1°-NCO) by 11 to 15 times, which is a dominant advantage. Usingthe selective isocyanate functional groups in steps of producingpolyurethane prepolymer, it benefits for easy operation in producingprocedures and the isocyanate prepolymer generated is valuable.

3. Triols cross-linking agent: Glycerol, Trimethylolpropane (TMP),1,2,6-Hexanetriol, Triethanolamine (TEA) and the like.

4. Ionic Center, such as dimethylolpropanic acid (DMPA),Dimethylolbutanoic acid (DMBA)

5. Aqueous PU Ambient Temperature Cross-Linking (Curing) Agent:

The aliphatic long chain carbon-carbon bond containing—PU oligomer andprepolymer is obtained from a process of the addition polymerization ofpolyols, polyisocyanates and ionic center (as an internal emulsifier,DMPA). Then proceed a process of neutralization with trialkylamine (e.g.triethylamine, TEA), and chain-extension with ethylenediamine duringwater dispersion. The internal ionic center within PU resin that havingstable micelles of PU particles formation that suspends in the aqueousPU dispersion. The latent PU cross-linking agent is added into theaqueous dispersion and it results in the formation of stable“cross-linking single-component aliphatic long chain carbon-carbon bondcontaining aqueous PU dispersion” (its pH value >8.0). The cross-linkingreaction takes place during drying process at ambient temperature or thepH value drops below 7.0.

This cross-linked PU resin owns the physical and chemical properties ofwater resistance, solvent resistance, mechanical strength and heatstability would be improved in large scale accordingly. By improving thecross-linking density to enhance the polymeric network structure of PUresin. This latent cross-linking agent (such as TMPTA-AZ) could betriggered the ring-opening reaction self-curing by lowering its pH valueof resin system. It is a convenient (single component), energy saving(at ambient temperature) cross-linking reaction takes place immediatelywhen the pH value of PU system lowers than 7.0. The common ambienttemperature cross-linking agents are listed as following:

6. Aliphatic Alcohols and Aliphatic Acids of Long Chain AliphaticCompounds:

[1] Octanol, C8, [2] 1-Nonanol, C9, [3] 1-Decanol, C10, [4] Undecanol,C11, [5] Dodecanol, C12, [6] 1-Tetradecanol, C14, [7] Cetyl alcohol,C16, [8] Stearyl alcohol, C18, [9] Arachidyl alcohol, C20, [10]Docosanol, C22, [11] Octanosol, C28, [12] Triacontanol, C30, [13]Policosanol, Cn

Aliphatic Acids

[1] Oleic acid, C18, [2] Ricinoleic acid, C18, [3] 12-Hydroxystearicacid, C18), [4] epoxidized oleic acid, C18

EXAMPLE 1 The Preparation of Isocyanate Terminated Polyurethane (PU)Prepolymer

Taking 13.4 g of 2,2′-bis(hydroxymethyl) propionic acid (DMPA) and 200 gof polytetramethylene ether glycol (PTMEG-2000) separately and placingthem into four-necked reaction tank, and heating to 140° C. to melt DMPAand stirring it with mechanical agitation evenly. Wait for thetemperature drop to 80° C., adding 0.1%(w/w) catalyst (T-12) and 66.6 gof isophorone diisocyanate (IPDI) and keep reaction temperature below86° C. with stirring until the reaction is completed (NCO % below thecalculated value). After the reaction is completed, processing NCOtitration to analyze the degree of reaction, as long as it reaches NCO %is less than 3% and remains at that value for one hour. Further usingFT-IR to determine the presence of the NCO peak (near 2267 cm⁻¹) inorder to make sure that if the reaction is completed.

EXAMPLE 2 Preparing Aliphatic Long Chain Carbon-Carbon Bond ContainingPU Oligomer

Using isocyanate functional groups having selective diisocyantes(polyisocyantes, IPDI)), triol (glycerol or trimethylolpropane, TMP) andlong chain fatty alcohol compounds (fatty alcohol or higher alcohol), byusing an excess amount of isocyanates (IPDI), and then adding minorcatalyst, dibutyltin dilaurate (DBTDL) to accelerate the reaction beingcompleted. It results in the formation of NCO-terminated aliphatic longchain carbon-carbon bond containing PU oligomer.

EXAMPLE 3 The Preparation of “Single-Component Aliphatic Long ChainCarbon-Carbon Bond Containing Aqueous PU Dispersion”

Selecting polyether polyol (e.g., PPG or PTMEG), polyisocyanate (IPDI)materials, or diol compounds containing hydrophilic functional groups asinternal emulsifier (for instance, dimethylol propanic acid, DMPA) andfatty alcohols (aliphatic long chain carbon-carbon bond alcoholcompounds). A long chain carbon-carbon bond containing PU prepolymerhaving isocyanate as terminal group (with fatty alcohols involved in thereaction). Determine the amount of NCO to confirm that the reaction iscompleted, and adding triethylamine to neutralize and adding deionizedwater with a chain extender (such as diethyleneamine) to process thesteps of chain extension and dispersion, and the self-emulsifiedaliphatic-containing aqueous PU dispersions is obtained. In this aqueousPU dispersion, adding proper quantity latent cross-linking agent(TMPTA-AZ or CX100) and maintain the pH value (>8.0) of aqueous PUdispersion. The stable “single-component cross-linking aliphatic longchain carbon-carbon bond containing aqueous PU dispersion” is formed.

EXAMPLE 4 The Preparation of “Self-Emulsified PDMS-Containing Aqueous PUDispersion”

Taking 180 g of polydimethylsiloxane (PDMS) diol (for instance, KF-6001)and 13.4 g of dimethylol propanic acid (DMPA, an internal ionic center)separately and placing them into four-necked reaction flask, and heatingto 140° C. to melt DMPA under vacuum and with constant mechanicalagitation for 4 hours. After cooling down to 50° C., then 0.2 g ofcatalyst (T-12) and 66.6 g of Isophorone diisocyanate (IPDI) are addedinto PDMS diol with agitation and keep the reaction temperature below86° C. until the reaction is completed (NCO % below the calculatedvalue). It results in a formation of PDMS-containing PU prepolymerhaving isocyanate as terminal groups. An aqueous mixture of de-ionizedwater of neutralizing agent (triethylamine, TEA) and chain-extender(ethylene diamine) is added into this PDMS-prepolymer slowly withagitation and “self-emulsified PDMS-containing aqueous PU dispersion” isobtained.

EXAMPLE 5 Cross-Linking PDMS/Oleic Containing Hydridizied PU Dispersions

The ratio of PDMS containing aqueous PU dispersion with oleic soap(oleic acid amine soap)

(PDMS/oleic) with 2/1, 1/1 and 1/2, are selected and mixing separately.Then TMPTA-AZ, a latent cross-linking agent (3 phr) is added into eachmixture as latent cross-linking agent. Each becomes “cross-linkingPDMS/oleic containing hydridizied PU dispersions”. After drying atambient temperature, it results in the formation of cross-linkedPDMS/oleic containing hybridized PU resin. Both PDMS and oleic acid arechemical bonded with hydrophobic PU resin. The dried cross-linkingPDMS/oleic hybridized hydrophobic PU resin is shown as the followingscheme 5.

Mixing PU/oleic acid mixed aqueous dispersion and aqueous PDMS-PUdispersion which are obtained from synthesis reaction by the ratio of2:1, 1:1 and 1:2, and then adding TMPTA-AZ cross-linking agent. Thedried cross-linking scheme is shown as the following scheme 5.

EXAMPLE 6 The Water-Repellent Treatment of Fiber for Room-TemperatureCross-Linking Oleic Acid-Contained and Polydimethylsiloxane(PDMS)Contained Mixing Aqueous Dispersion

Following Example 5, diluting the cross-linking PDMS/oleic containinghybridized PU dispersion with de-ionized water to proper concentration(5-10% of solid). Then apply it on the surface of fabric to carry outthe hydrophobic treatment. It is cross-linked and forminginterpenetrating polymeric network (IPN) structures and anchored intofabric after drying. That improves the bonding strength between treatedPU resin and fabric that improve washing durability and solventresistance of hydrophobic treated fabrics.

Please refer to Table 1. Shown as the SEM micrographs (FIG. 1 and FIG.3) and EDS (FIG. 2 and FIG. 4), it proves that the treatment on thesurface of fabric by the cross-linked PDMS/oleic containing hybridizedPU resin of the present invention can maintain over 85% originalhydrophobic property (water-repellent efficacy) after 40 washing cycles,furthermore, it is found that there are silicon of PDMS stays on thesurface of fabric (EDS).

TABLE 1 The hydrophobic property of the fiber surface treated by aqueousPU dispersion containing aliphatic acid and PDMS mixed (washed 40 times)PDMS/oleic ratio of hybridized PU resin 2/1 1/1 1/2 Water drop contactangle on 125.0 128.3 135.3 treated fabrics (°) Sliding angle of waterdrops (°) 18.8 17.8 17.8 on treated fabric surface Time for water dropsstay on >60 >60 >60 treated fabrics (min)To sum up the aforementioned description, the non-fluoro hydrophobicPDMS/oleic containing hybridized PU (polyurethane) resin of the presentinvention can have long lasting hydrophobic property after 40 washingcycles of treated fabrics. By cross-linking reaction to improve thecross-linking density of hydrophobic PDMS/oleic containing hybridized PUresin of the present invention, it has improved the property of washingdurability (resistance) and solvent resistance. Besides, the PU resin ofthe present invention has no fluoro and the water repellent treatmentwith less energy requirement which comply with the non-toxicrequirements and provision of components used in fabrics in the futureto people nowadays. The present invention comparing to prior waterrepellent which uses fluoro compounds has superior efficacy.

1. A non-fluoro hydrophobic aqueous polyurethane dispersion, which isproduced by a method comprises the following steps: selecting a compoundcomprising alcohols, amines, carboxylic acids, saturated ordouble-bonded or epoxidized aliphatic groups or polydimethylsiloxanecomprising alcohol groups, amino groups, oxosilane to be reacted withpolyisocyante to obtain a polyurethane prepolymer having isocynate (NCO)terminal group; adding a compound having hydrophilic functional groupsinto the polyurethane prepolymer having isocyanate terminal groups,after neutralizing, adding water to disperse the polyurethane prepolymerto form an aqueous polyurethane dispersion; and adding aroom-temperature cross-linking agent into the aqueous polyurethanedispersion to obtain a self-crosslinked aqueous polyurethane dispersion.2. The aqueous polyurethane dispersion according to claim 1, wherein thepolyurethane-dispersion can be made into single-liquid form.